Insulated electrical conductors having corona resistant polymeric insulation containing organo metallic compounds

ABSTRACT

INSULATED ELECTRICAL CONDUCTORS HAVING IMPROVED CORONA RESISTANCE COMPRISING A METAL CONDUCTOR SURROUNDED BY A MAJOR PORTION OF A DIELECTRIC POLYMER CONTAINING INTERMIXED THEREWITH A MINOR AMOUNT OF AN ORGANO-METALLIC COMPOUND OF A METAL SELECTED FROM SILICON, GERMANIUM, TIN, LEAD, PHOSPHOROUS, ARSENIC, ANTIMONY, BISMUTH, IRON, RUTHENIUM AND NICKEL AND A METHOD FOR THE PREPARATION OF THE INSULATED ELECTRICAL CONDUCTORS.

United States Patent INSULATED ELECTRICAL 'CONDUCTORS HAVING CORONA RESISTANT POLYMERIC INSULA- TION CONTAINING ORGANO METALLIC COM- POUNDS James J. McKeown, Mahtomedi, Minn., assignor to Minnesota Mining and Manufacturing Company, St. Paul, Minn.

N0 Drawing. Continuation-impart of application Ser. No. 555,695, June 7, 1966. This application Nov. 14, 1968, Ser. No. 775,958

Int. Cl. C08f 45/62; C08g 51/62; H01b 3/28 US. Cl. 252-635 49 Claims ABSTRACT OF THE DISCLOSURE Insulated electrical conductors having improved corona resistance comprising a metal conductor surrounded by a major portion of a dielectric polymer containing intermixed therewith a minor amount of an organo-metallic compound of a metal selected from silicon, germanium, tin, lead, phosphorous, arsenic, antimony, bismuth, iron, ruthenium and nickel and a method for the preparation of the insulated electrical conductors.

This is a continuation-in-part of the copending application Ser. No. 555,695, filed June 7, 1966, now abandoned.

The present invention relates to methods for the preparation of corona resistant insulated electrical conductors and to the insulated conductors themselves.

[In certain environments solid dielectric materials which are used to insulate electrical conductors are subject to voltages in excess of the corona starting voltage during operation (e.g. in certain electric motor applications). In such cases, the life of the dielectric is greatly reduced by failure due to corona breakdown, particularly when the dielectric is a solid polymer. Thus improvements in the resistance to corona of polymeric materials is muchto be desired.

A specific problem is the resistance to corona of organic polymer dielectric materials in high voltage applications in which there is a gap over which corona discharges can occur (e.g. greater than about one mil) between the dielectric and the conductor or a void within the material itself. Under such conditions, the life of dielectric materials is often much shorter than under the same conditions where there is no such gap or void and a dielectric which will retain its electrical insulation properties for longer periods of time under such conditions is also to be desired.

Accordingly, it is an object of the present invention to provide new insulated electrical conductors having improved resistance to corona and of improved breakdown strength.

It is another object of the invention to provide a method for preparing insulated conductors of improved resistance to corona and of improved breakdown strength.

It is a further object of the invention to provide electrical conductors coated with compositions which have relatively long corona lives.

It is a further object of the invention to provide electrical insulation materials which are useful in applications in which they are subject to high voltages for extended periods of time.

It is a further object of the invention to provide a method for providing a high voltage and corona resistant insulation on an electrical conductor.

Other objects of the invention will become apparent to those skilled in the art upon reading the following specification.

"ice

The present invention relates to a method for improving the voltage endurance and corona resistance of a solid dielectric organic polymer selected from polyacrylics, polydienes, polyvinyls, polyolefines, polyesters, polyethers, polyarnides, polysulfones, polycarbonates, polysulfides, polyepoxides, polyureas and polyurethanes and copolymers thereof. The organic dielectric polymers useful in the invention contain recurring carbon atoms in the main chains thereof and normally contain recurring carbon-carbon bonds in the main chains. The main chains of the polymers contain a major proportion of carbon atoms, i.e. at least half of the atoms in the main chains are carbon atoms.

The improvement in the voltage endurance and corona resistance of these polymers is accomplished by mixing with the polymer a minor amount of an organo-metallic compound (preferably from about 0.1 to 20 percent based upon the final weight of the polymer). The organometallic compound includes a metal selected from a class of elements of Groups lV-B, V-B and VHI of the Periodic Table of Elements having atomic numbers from 14 to 83 inclusive, said metal being bonded through carbon to the organic portion of the molecule. The organometallic compound is intimately intermixed with and is preferably dissolved in the polymer. The Periodic Chart of the Elements referred to herein is published inside the back cover of the text Chemistry of Organic Compounds by Carl R. Noller, reprinted August 1952, and published by the W. B. Saunders Company, Philadelphia, Pa. The metals of particular interest included in the foregoing class are silicon, germanium, tin, lead, phosphorous, arsenic, antimony, bismuth, iron, ruthenium and nickel. The invention also relates to a method of making an insulated electrical conductor suitable for high voltages and of improved corona resistance which comprises forming about an electrical conductor the mixture of the polymer and the organo-metallic compound and to the insulated electrical conductors themselves.

There are one or more metal atoms in the organometallic compounds which are suitable for use in the present invention, but usually not more than two. There can be a maximum of five full bonds or the equivalent thereof between any metal atom and carbon atoms in the organic groups, preferably from two to four such bonds. In most cases these are full bonds between one carbon atom and one metal atom. In some cases, however, the bonds are shared by more than one carbon atom. Thus in ferrocene the equivalent of two full bonds with a single metal atom are shared equally by ten carbon atoms (pi bonding). The organic group or groups can be aromatic, aliphatic or araliphatic. The metal atom can have one or more (usually not more than 2) electronegative groups covalently or ionically bonded to it in the organo-metallic compound although this is not necessary. Such electronegative groups include oxide, halide, sulfide, hydroxide, etc.

Preferably, the organometallic compound is added in the amount of from about 0.1 to 20 percent by weight of the polymer. Lesser amounts of the additive are insufficient to have a desired effect and greater amounts thereof are unnecessary. Ordinarily, from about 1 to 20 percent of additive (based on the weight of the final polymer) is utilized and from about 1 to 10 percent is preferred. The polymer additive mixture is solid at ordinary temperatures, e.g. 20 C. and normally at the operating temperature of the device in which it is used.

The technique for incorporating the organo-rnetallic compound into the insulating organic polymer depends on properties of the polymer. It can be readily milled into elastomers (with conventional milling equipment), mixed into liquid polymers or polymer solutions (such as liquid epoxy or other resins, thermoplastic melts or solutions), mixed with a powdered polymer, etc. Conversion by weight unless otherwise specifically indicated. The

to the desired shape and form can be accomplished by an word mil herein indicates 0.001 inch. appropriate technique such as by extrusion, casting, mold- Corona life tests of the compositions of the invention ing (e.g. compression molding or injection molding), catand the controls prepared in the same way as the lots of ing, etc. In some cases it will also be necessary during the invention but containing no organo-metallic comconversion to cure and/or remove volatiles from the pound were run on these films utilizing the following propolymer. cedure: The sample to be tested (in film form) was laid An alternate technique which can be used is to coat upon a grounded flat copper plate. The high voltage electhe surface of a film of the polymer with the organotrode (a A by A" rectangular plate of transformer metallic compound (often the surfaces of several thin core iron) was placed on top of the test film. The copper films are coated then stacked). A glow discharge can, for plate and the film being tested both extended beyond the example, be used for forming a highly insulating yet periphery of the high voltage electrode on all sides. The

corona resistant coating on the film. This technique is corona discharges occurred largely from the edges of the usually used when the polymer is such that its processing high voltage electrode to the test film. Five replicate conditions might result in the decomposition of the organo- 5 tests were run on each film. The tests were run at 1,042 metallic compound (e.g. polytetrafluoroethylene). cycles per second (c.p.s.), at room temperature (25 C.)

Among the organo-metallic compounds which can be and at 2500'volts. The effect of the relative humidity on used in the practice of the invention are aryl and/ or alkyl the tests was eliminated by running them at zero persilane compounds such as triphenyl silane, aryl and/or cent relative humidity. The test time to failure of the alkyl germanium compounds such as triphenyl germane; third (median) sample of each replicate set was recorded. aryl and/or alkyl tin compounds such as tetraphenyl tin, The test time of the third sample to fail was then reduced his tributyl tin oxide, tributyl tin chloride and dibutyl tin to equivalent 60' cycles per second (c.p.s.) by multiplying dichloride; aryl and/or alkyl lead compounds such as by 17.4 (1,042/60). tetraphenyl lead; aryl and/or alkyl phosphorous com- Plus signs in the data indicate that failure had not ocpounds such as triphenyl phosphorous; aryl and/ or alky curred at the time the final readings were taken for the arsenic compounds such as triphenyl arsenic oxide; aryl tables and that the tests were continued thereafter. The and/or alkyl antimony compounds such as triphenyl anticontrol values shown have been adjusted to the same mony dichloride; aryl and/or alkyl bismuth compounds electrical stresses as the respective lots of the invention so such as trinaphthyl bismuth; biscyclo pentadienyl iron that direct comparisons of the corona lives (i.e. time to (ferrocene) and derivatives thereof such as acetyl ferro- 3O corona breakdown) can be made. cene; etc.

The polymers which can be used in the practice of the EXAMPLE 1 invention are polyacrylics, polydienes, polyvinyls, poly- Elastomeric polymers olefines, polyesters, polyethers, polyamides, polysulfones, polycarbonates, polysulfides, po1yepoxides,polyureas and The lots of this example were prepared as follows:

polyurethanes and copolymers thereof. Included in the Twenty-five grams of elastomer were banded together on foregoing classes are polybutadienes, polyisoprenes, polya conventional laboratory rubber mill. No additional heat chloroprenes, polystyrenes, polyisobutylenes, polyvinylwas supplied although the elastomer became Warm due to chlorides, polyacrylonitriles, polychlorosulfonated ethylthe heat of working. One and one quarter grams of the enes, polyethylenes, polypropylenes, polytetra-fiuoroethyldesired organometallic compound were added to the enes, allyl resins, alkyd resins, cellulose esters (e.g. cellubanded elastomer and milling was continued until the lose acetates), chlorinated polyethers, amino resins (e.g. mass appeared to be uniform. Twenty minutes normally prepared from urea, melamine and formaldehyde), cowas required to accomplish uniform distribution of the polymers of lower alkylenic monomers such as ethylene organometallic compound. The elastomer was remoxed and propylene, copolymers of styrene and butadiene, cofrom the mill and cut into small pieces which were subsepolymers of vinylidene fluoride and hexafluoropropene, quently compression molded at 300 F. for one minute copolymers of acrylonitrile, butadiene and styrene, etc. to the desired film thickness. The elastomers were pressed The foregoing include elastomeric and non-elastomeric between sheets of aluminum although polytetrafluoropolymers of the types included in the examples herein. ethylene film was inserted between the aluminum and elas- Both thermoplastic and thermosetting polymers can be tomer where needed to effect easy release of the clasused. Preferably, the polymers are halogen free. tomeric film. The control samples were milled and com- The following examples are offered to furnish a better pression molded in the same manner. The compositions understanding of the present invention, and are not to and test results of the various lots are given in the folbe construed as in any way limiting thereof. All parts are lowing tables:

Elastomer organometallic Lot No. Type Manufacturing company Trade designation additive 1 Polyacrylic B. F. Goodn'eh Chemical Company Hycar polymer 4021 Tm'phenyl silane. 2 Polyacrylonitrile .do Hycar polymer 1001..- Trinaphthyl antimony. 3--.; Polyurethane .-d0 Estone polymer Dicyclopentadienyl 570311 nickel. 4 Polyisoprene Goodrich-Gulf Chemical Company, Inc Arsnlelripol polymer 7 Acetyl ferroeene. 5 Polyehloroprene E. I. du Pont de Nemours and 00., Inc Nai igrene polymer Triphenyl arsenic. 6 Polychlorosulionated ethylene do Hypalon polymer 40 Dibutyl tin sulfide. 7 Polyisobutylene Enjay Company, Inc Vistanex polymer 200.- Triphenyl bismuth. 8 Copolymer of ethylene and propylene do EP R polymer 404... Trikplhenlyl lead c on e. 9 Polybutadiene Phillips Petroleum Company Trans polymer 4 Ferrocene. 10-.- Copolymer of styrene and butadiene Texas-US. Chemical Company-.. Symbol polymer 1502 Dicyghlopentadienyl ru enium. 11...- Polysulfide Thiokol Chemical Corporation Thiokol polymer ST Bis tributyl tin oxide. 12 Copolymer oi vinylidene fluoride and Minnesota Mining and Manufacturing Company- Fluorel polymer 2l40 Triphenyl phosphine.

hexafiuoro propane.

EXAMPLE %5%?;%E;Y5 Increasem One gram of ferrocene was dissolved in 20 grams of a E t 1 1 1 r fi gg liquid epoxy resin and the resin was poured upon a glass 5.2:. $1, 11 t v plate which had been previously coated with a release (volts/mil) Control additi percent 5 agent. Twenty-five mil shims were placed on the plate and another coated plate was placed on top of the resin.

100 230 960 317 The resin was cured at 170 F. for 16 hours. A control 96 110 1, 560 1, 320 100 727 2,450 238 sample without the organometallic compound was prelgg 3 538 pared in a similar manner. The corona life of the resin 100 447 5 3 without the additive was 835 60-cycle hours at 100 volts/ lgg 1 Egg itiggi mil and room temperature whereas the resin with the 100 21210 additive lasted 7830 60-cycle hours under similar condi- 100 2, 500 8,350 234 104 9 47 422 tions for an improvement of 840% 100 148 412 178 EXAMPLE 6 Low density polyethylene (Dow 1705) was hot milled EXAMPLE 2 with the appropriate quantity of triphenyl antimony so Thermoplastic polymers the final concentration was 1, 3 or 5%. A control sample These polymers were also processed on a hot mill. The g 9 i q fi g g g falied ,2. mill was preheated to 250 F. and grams of the polyg e i 3 1 any 3 mer was added and banded together on the mill. One a i een on es or more an ours W1 and one quarter grams of the appropriate organometallic any ures- EXAMPLE 7 was then added and milling continued until the material appeared uniform. The mixture was cut into smaller 25 A S-mil film of polytetrafluoroethylene was placed bepieces which were subsequently compression molded into tween two halve of a resin flask and acu t d t a re- 0.025 thick films at 300 F. Sheets of aluminum were duced pressure on both sides. Ferrocene which had been placed on either side of the material during pressing in previously placed in one chamber was vaporized at the order to assure a smooth, flat surface on the film. A conreduced pressure. The voltage between two electrodes, trol without the organometallic compound was processed which had also been previously placed within the resin in a similar manner. The compositions and test results fla k, was increased until a glow discharge developed. of the various lots are given in the following tables: The glow discharge caused the fcrrocene vapor to form Polymer Organometallic Lot No. Type Manufacturing company Trade designation additive 1 Polyethylene Dow Chemical Company Dow polymer 1705 Triphenyl arsenic. 2 Polyacrylate E. I. du Pont de Nemours and 00., Inc Lucite polymer 147 Triphenyl silane.

Acrylouitrile butdiene styrene terpolymer Monsanto Chemical Company 'Lustran I polymer 610.-- Bis(tributyl tin) oxide. 4 Cellulose acetate Eas man Teni e Company 32806H6 Triphenyl antimony oxide. 5 P l styre e Dow Chemical Com a St 1 47 h 1; 6 P lgvinyl chlorlde Monsanto Chemical o n i panyn 0351331312515551058-009- gfz lz ra t y l lz i ni 7 Chlorinated polyether Hercules Powder Company Penton polymer 9215E Acetyl ferrocene.

Comname equivalent, a tough coating which adhered to the polytetrafluoro- 60 c.p.s. (hours) Iucreaseln ethylene. This coating derived from ferrocene was highly Electrical gg g 5 insulating. Films of the coated polytetrafluoroethylene stress additive, were stacked to a total thickness of 25-mil, with the (volts/mil) Control additive percent coated sides facing the active electrode and the corona resistance measured and compared with a control. The

g8 .53% 8.9 33 gg corona life of the polytetrafluoroethylene with the 100 3,230 7,900 1 50 coating was 57-00 60-cycle hours whereas the control 1% 3 3.2;8 5 failed in 410 60-cycle hours to give an improvement of These insulations with improved corona resistance EXAMPLE3 are highly useful in electric motors and generators,

cables such as power transmission cables, ca acitors, Twenty-f ve grams f P y y "Ftraphthalate was transformers and other such electric equipmen t where pulverized into a powder and mixed with 1.25 grams of high voltages are normally encountered tetraphenyl tin. A small quantity of the mixed powder Whatis claimed is: was compression molded be sheetsof alummuln at 1. In an insulated electric device suitable for high volt- 520 F. The sample was cooled and cut into small pleces ages, com risin an electric conductor a h k d d fil Th d p g me ns and an elec whic were St C e all Presse Into a 15 Proce tric insulator in insulating proximity thereto, the follow- Was repeated 1mm m PP umform- A control ing improvement serving to provide improved corona sample was prepared in a slmllaf manner- The Corona hfe resistivity, said conductor means being insulated with a of the congrol ellt i1 0 Volta/H111 il T001111 f g solid dielectric organic polymer selected from the group was 960 6 'Fy 6 0111's W ereas t e P Y wlt t e consisting of polyacrylics, polydienes, polyolefines, polyorganometallic compound lasted 6100 60-cycle hours for esters, polyethers, polyamides polysulfones p01ycarbo an improvement of 535 nates, polysulfides, polyepoxides, polyureas and poly- EXAMPLE 4 urethanes and copolymers thereof, said polymer contain- Twenty five grams of Hercules Profax 6 523 polypropylmg ultimately mtermged Fherevj/lth from.abol.lt 1 to 20 ene with 1.25 grams triphenyl bismuth was prepared percent of an aromatic, aliphatic or araliphatic organocording to the procedure of Example The corona life metallic compound based upon the Weight of the polymer of the control at volts mil-1 and room temperature was where the organometallic compound includes a metal se- 1640 ,60 cyc1e hours where the polypropylene i h lected from the class consisting of silicon, germanium,

triphenyl bismuth lasted 20,100 hours for an improvefi lead, P p arsenic, ony, bismuth, iron, merit of 1130%. ruthenium and nickel, each organic group in the organometallic compound being bonded directly through carbon to the metal therein.

2. An insulated device according to claim 1 wherein the organometallic compound contains silicon.

.3. An insulated device according to claim 1 wherein the organometallic compound contains tin.

4. An insulated device according to claim 1 wherein the organometallic compound contains lead.

5. An insulated device according to claim 1 wherein the organometallic compound contains phosphorus.

6. An insulated device according to claim 1 wherein the organometallic compound contains arsenic.

7. An insulated device according to claim 1 wherein the organometallic compound contains antimony.

8. An insulated device according to claim 1 wherein the organometallic compound contains bismuth.

9. An insulated device according to claim 1 wherein the organometallic compound contains iron.

10. An insulated device according to claim 1 wherein the organometallic compound contains ruthenium.

11. An insulated device according to claim 1 wherein the organometallic compound contains nickel.

12. An insulated device according to claim 1 wherein the organometallic compound contains an electronegative group bonded to the metal therein.

13. An insulated device according to claim 1 wherein the dielectric polymer is a polyacrylic.

14. An insulated device according to the dielectric polymer is a polydiene.

15. An insulated device according to the dielectric polymer is a polyolefine.

16. An insulated device according to the dielectric polymer is a polyester.

17. An insulated device according to the dielectric polymer is a polyether.

18. An insulated device according to the dielectric polymer is a polysulfide.

19. An insulated device according to the dielectric polymer is a polyepoxide.

20. An insulated device according to the dielectric polymer is a polyurethane.

21. An insulated device according to the dielectric polymer is halogen-free.

22. An insulated device according to the dielectric polymer is a polyethylene.

23. An insulated device according to claim 1 wherein the dielectric polymer is a copolymer of ethylene and propylene.

24. An insulated electrical conductor having improved resistance to corona comprising a metal conductor insulated by a solid dielectric organic polymer selected from the group consisting of polyacrylics, polydienes, polyolefines, polyesters, polyethers, polyamides, polysulfones, polycarbonates, polysulfides, polyepoxides, polyureas and polyurethanes and copolymers thereof, said polymer containing intimately intermixed therewith from about 1 to percent of an aromatic, aliphatic or araliphatic organometallic compound based upon the weight of the polymer where the organometallic compound includes silicon, each organic group in the organometallic compound being bonded directly through carbon to the silicon therein.

25. An insulated electrical conductor having improved resistance to corona comprising a metal conductor insulated by a solid dielectric organic polymer selected from the group consisting of polyacrylics, polydienes, polyolefines, polyesters, polyethers, polyamides, polysulfones, polycarbonates, polysulfides, polyepoxides, polyureas and polyurethanes and copolymers thereof, said polymer containing intimately intermixed therewith from about 1 to 20 percent of an aromatic, aliphatic or araliphatic organometallic compound based upon the weight of the polymer where the organometallic compound includes antimony, each organic group in the organometallic compound being bonded directly through carbon to the antimony therein.

claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein claim 1 wherein 26. An insulated electrical conductor'having improved resistance to corona comprising a metal conductor insulated by a solid dielectric organic polymer selected from the group consisting of polyacrylics, polydienes, polyolefines, polyesters, polyethers, polyamides, polysulfones, polycarbonates, polysulfides, polyepoxides, polyureas and polyurethanes and copolymers thereof, said polymer containing intimately intermixed therewith from about 1 to 20 percent of an aromatic, aliphatic or araliphatic organometallic compound based upon the weight of the polymer where the organometallic compound includes iron, each organic group in the organometallic compound being bonded directly through carbon to the iron therein.

27. In a method of making an insulated electrical conductor suitable for high voltages and of improved corona resistance, the improvement which comprises forming about an electrical conductor a solid mixture of a solid dielectric organic polymer selected from the group consisting of polyacrylics, polydienes, polyolefines, polyesters, polyethers, polyamides, polysulfones, polycarbonates, polysulfides, polyepoxides, polyureas and polyurethanes and copolymers thereof and from about 1 to 20 percent of an aromatic, aliphatic or araliphatic organometallic compound based upon the weight of the polymer where the organometallic compound includes a metal selected from the class consisting of silicon, germanium, tin, lead, phosphorous, arsenic, antimony, bismuth, iron, ruthenium and nickel, each organic group in the organometallic compound being bonded directly through carbon to the metal therein.

28. A method according to claim 27 wherein organometallic compound contains silicon.

29. A method according to claim 27 wherein organometallic compound contains tin.

30. A method according to claim organometallic compound contains lead.

31. A method according to claim 27 wherein organometallic compound contains phosphorus.

32. A method according to claim 27 wherein organometallic compound contains arsenic.

33. A method according to claim 27 wherein organometallic compound contains antimony.

34. A method according to claim 27 wherein organometallic compound contains bismuth.

35. A method according to claim 27 wherein organometallic compound contains iron.

36. A method according to claim 27 wherein organometallic compound contains ruthenium.

37. A method according to claim 27 wherein organometallic compound contains nickel.

38. A method according to claim 27 wherein the organometallic compound contains an electronegative group bonded to the metal therein.

39. A method according to claim 27 dielectric polymer is a polyacrylic.

40. A method according to dielectric polymer is a polydiene.

41. A method according to dielectric polymer is a polyolefine.

42. A method according to dielectric polymer is a polyester.

43. A method according to dielectric polymer is a polyether.

44. A method according to dielectric polymer is a polysulfide.

45. A method according to claim dielectric polymer is a polyepoxide.

46. A method according to claim dielectric polymer is a polyurethane.

47. A method according to claim dielectric polymer is halogen-free.

48. A method according to claim dielectric polymer is a polyethylene.

the

the

27 wherein the the the

the

the

the

the

the

wherein the claim 27. wherein the claim 27 wherein the claim 27 wherein the claim 27 wherein the claim 27 wherein the 27 wherein the 27 wherein the 27 wherein the 27 wherein the dielectric polymer is a copolymer of ethylene and propylene.

References Cited UNITED STATES PATENTS McKeown et al. 117128.4 Dietz 117232 Mack 26045.75 Garner 26045.7X

Heiberger et a1. 26045.75X

5 JOHN T. GOOLKASIAN, Primary Examiner M. E. MCCAMISH, Assistant Examiner US. Cl. X.R.

Barnes et a1 1172 2 10 117-232; 174-110.44; 25263.2; 26045.75 

